Co-cured gel coats, elastomeric coatings, structural layers, and in-mold processes for their use

ABSTRACT

Co-cured urethane and vinyl ester, epoxy, or unsaturated polyester gel coats having improved toughness and flexibility compared with conventional polyester gel coats are disclosed. The gel coats, which have 10-50 wt. % urethane content, adhere well to structural layers and can be used in a traditional in-mold process. Co-cured elastomeric coatings comprising from 50 to 95 wt. % of a urethane component and an unsaturated polyester, epoxy, or vinyl ester are also disclosed. Unlike conventional urethane coatings, the elastomeric coatings adhere well to structural layers and can be used in a traditional in-mold process. Castings or structural layers comprising a reinforced thermoset of co-cured urethane and vinyl ester, epoxy, or unsaturated polyester components, including 10-95 wt. % of the urethane component, are also described. The invention includes in-mold processes for making laminates that utilize the gel coats, elastomeric coatings, and/or structural layers. The in-mold process gives flexible, durable, urethane-containing laminates having good interlayer adhesion.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application, filed under 35 U.S.C. § 120, is a continuationapplication of Ser. No. 13/743,203, now U.S. Pat. No. 9,371,468 issuedon Jun. 21, 2016, which was filed on Jan. 16, 2013, and for which adivisional application Ser. No. 15/158,411 was filed on May 28, 2016.The disclosures of each of the foregoing are expressly incorporatedherein by reference.

FIELD OF THE INVENTION

The invention relates to coatings and structural layers commonly used tofabricate molded products, and in particular to co-cured systems havingimproved adhesion, toughness, flexibility, and structural performance.

BACKGROUND OF THE INVENTION

Gel coats are used in marine and other applications to provide a smooth,attractive surface to the exterior of fiberglass-reinforced products andto protect laminates from the environment. A gel coat is a surfacecoating that usually contains pigments, resin, fillers, thixotropicagents, UV stabilizers, and promoters. When applied to a mold surface,it cures with structural layers and reproduces contours of the moldsurface while sealing in layers of reinforcing fiber. Most gel coats areformulated using unsaturated polyester, vinyl ester, or epoxy resins.When high performance is needed (as in marine or shower/bathapplications), unsaturated polyester resins made from isophthalic acid,maleic anhydride, and neopentyl glycol are often selected.

In a typical in-mold process, a gel coat is sprayed or brushed onto amold surface and allowed to partially cure. A skin coat of resin isapplied and cured, and then structural layers that contain fiberreinforcement are subsequently applied.

Although unsaturated polyester and vinyl ester gel coats are widelyused, they tend to be relatively brittle. Because of their lack oftoughness, the coatings can crack or chip. In fact, gel coat-relatedissues account for about half of recreational boat warranty claims.

Polyurethane or polyurea coatings are sometimes used as an alternativeto a polyester gel coat. Urethanes offer the potential advantages ofimproved flexibility and toughness. However, urethanes need to beapplied after manufacture. When urethanes are applied in-mold as gelcoats, the unsaturated polyester-based structural layers do not adherewell enough to the gel coat. In some cases, it is possible to use afiber tie coat to create a mechanical bond. For instance, anincompletely saturated spun-bonded polyester fabric can be placed intothe uncured urethane coating and allowed to cure, followed by infusionwith resin and lamination with structural layers. Here, the unsaturatedfabric acts as a mechanical interface between the coating and structurallayers. However, although this provides desirable adhesion, it is laborintensive, and in large parts, gaining access to place the tie-coat canbe problematic.

Unsaturated polyester structural layers do not bond well to curedurethanes, and even post-applied urethane coatings can delaminate orpeel, particularly under hydrodynamic conditions (as in a speedboat). Noracer wants to cross the finish line in last place, but especially notwhile also towing an unsightly “bag” of seawater. Thus, despite thepotential flexibility and toughness of urethanes, they have notdisplaced traditional unsaturated polyester gel coats.

“Hybrid” urethane/polyester systems were developed in the early 1980s atAmoco and were subsequently popularized elsewhere (see, e.g., U.S. Pat.Nos. 4,280,979; 4,822,849; 4,892,919; 5,153,261; 5,159,044; 5,296,544;5,344,852). Most of these disclosures focus on foams or molded systems,with less emphasis on gel coats, although there is some use of hybridsystems for gel coating (see U.S. Pat. Appl. Publ. Nos. 2007/0049686 and2008/0160307). The prototypical hybrid system has two components: an “Aside,” which is a mixture of a polyisocyanate and methyl ethyl ketoneperoxide (MEKP, a part of the catalyst used to cure the unsaturatedpolyester resin); and a “B side,” which includes a hydroxyl-terminatedunsaturated polyester polyol, styrene, fillers, pigments, a glycol chainextender, a cobalt compound (the other half of the polyester curative),and a tin catalyst (urethane catalyst). When the A and B sides arecombined, both polyurethane and polyester curing reactions occur. Thehydroxyl-terminated unsaturated polyester polyol participates in bothcuring processes, as its hydroxyl groups react with the polyisocyanateand its carbon-carbon double bonds react with styrene and the radicalcurative.

Each of the hybrid systems discussed above requires the synthesis anduse of a hydroxyl-terminated unsaturated polyester polyol, a materialthat is not normally used in either a conventional polyurethane (whichuses saturated polyether or polyester polyols) or polyester system(which has unsaturation but not substantial hydroxyl end group content).

Hybrid systems are still available to a limited degree commercially,although in an evolved form. For instance, CCP Composites sells productsunder the Xycon® mark for use in pultrusion that are “modifiedthermosetting acrylic resins containing styrene monomer.” These arecombined with an aromatic prepolymer to produce tough, heat andwater-resistant polymers. Hydroxy functionality is frequently introducedby using hydroxyacrylate monomers (hydroxyethyl acrylate, hydroxyethylmethacrylate), which can be pricey. For some disclosures ofurethane/acrylate systems, see U.S. Pat. No. 7,150,915 or U.S. Pat.Appl. Publ. No. 2007/0001343.

Co-cured systems of urethanes and polyesters have been described,frequently in the context of academic papers related to the study ofproperties of interpenetrating networks (IPNs). For just two examples,see X. Ramis et al., Polymer 42 (2001) 9469 or G. Y. Wang et al., Eur.Polym. J. 36 (2000) 735. As noted in the latter paper, a true IPN doesnot have chemical bonds between the networks, but a co-cured systeminvolving commercial urethane and polyester systems would have somereaction of urethane —NCO groups with polyester —OH groups.

U.S. Pat. No. 5,952,436 describes a co-cured product made by reactingstyrene, a polyisocyanate, and a polyetherester resin. Thepolyetherester resin is made by inserting maleic anhydride into C—Obonds of a polyether polyol.

U.S. Pat. No. 5,936,034 combines a traditional unsaturated polyester gelcoat, though incompletely cured, and a co-cured “backer” layer made froman unsaturated polyester resin and an isocyanate-terminated prepolymer.

Despite the wealth of literature related to hybrid systems and IPNs,relatively little commercial success has been achieved with co-curedurethane and unsaturated polyester/vinyl ester resins. Most gel coatsare still applied as in-mold coatings with unsaturated polyester resins,and most urethanes are applied as post-manufacture coatings. The issuesof relatively poor adhesion between these traditional systems have yetto be completely resolved.

The industry would benefit from the availability of gel coatings thathave improved toughness, flexibility, and chip- or crack-resistancecompared with unsaturated polyester gel coats. Preferably, thesebenefits could be achieved without sacrificing good adhesion tostructural layers or the convenience of using an in-mold coatingprocess. Ideally, the gel coat could be formulated with commerciallyavailable materials, thereby overcoming the need to synthesize a specialreactant, as is used in the hybrid systems discussed above. The industrywould also value elastomeric coatings having improved adhesion tostructural layers and a reduced tendency to delaminate from themcompared with traditional urethane coatings. Ideally, the elastomericcoating could be used in an in-mold process. Finally, the industry wouldbenefit from the ability to fabricate fiber-reinforced structural layersthat can adhere well to coatings and to each other. Preferably, theselayers could also have varying degrees of strain to failure, toughness,stiffness, or flexibility. The ability to “dial in” properties for eachlayer in a laminate would be valuable.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to a gel coat comprising co-curedurethane and vinyl ester, epoxy, or unsaturated polyester components.The urethane component is from 10 to 50 wt. % based on the amount of gelcoat, and the urethane and vinyl ester, epoxy, or unsaturated polyesterreactants are combined under conditions effective to cure bothcomponents in the same cure cycle. The gel coats have improved toughnessand flexibility compared with conventional polyester gel coats, theyadhere well to structural layers, and they can be used in a traditionalin-mold process.

In another aspect, the invention relates to an elastomeric coatingcomprising co-cured urethane and vinyl ester, epoxy, or unsaturatedpolyester components. The urethane component is from 50 to 95 wt. %based on the amount of elastomeric coating. The urethane and vinylester, epoxy, or unsaturated polyester reactants are combined underconditions effective to cure both components in the same cure cycle. Theelastomeric coatings are flexible and tough, they adhere well tostructural layers, and unlike conventional urethane coatings, they canbe used in a traditional in-mold process.

In another aspect, the invention relates to a casting which comprisesco-cured urethane and vinyl ester, epoxy, or unsaturated polyestercomponents. The urethane component is from 10 to 95 wt. % based on theamount of casting. The urethane and vinyl ester, epoxy, or unsaturatedpolyester reactants are combined under conditions effective to cure bothcomponents in the same cure cycle.

In yet another aspect, the invention relates to a structural layercomprising a reinforced thermoset. The thermoset comprises co-curedurethane and vinyl ester, epoxy, or unsaturated polyester components.The urethane component is from 10 to 95 wt. % based on the amount ofthermoset. The urethane and vinyl ester, epoxy, or unsaturated polyesterreactants are combined under conditions effective to cure bothcomponents in the same cure cycle.

The invention also includes in-mold processes for making laminates. Inone process, a gel coat of the invention is used; in another, anelastomeric coating of the invention is used. In each process, a gelcoat or elastomeric coating of the invention is first applied to a mold.Before or after the gel coat or elastomeric coating layer cures, atleast one structural layer is applied, and the layers are allowed tocure to produce the laminate. In another in-mold process of theinvention, a conventional gel coat is applied first. Before or after thegel coat layer cures, at least one inventive structural layer comprisinga reinforced thermosetable composition is applied, and the layers areallowed to cure to produce the laminate.

DETAILED DESCRIPTION OF THE INVENTION

Generally, the invention relates to coatings and structural layers usedto fabricate molded products, and in particular to co-cured systemshaving improved adhesion, toughness, and flexibility.

In one aspect, the invention relates to a gel coat. The gel coatcomprises co-cured urethane and vinyl ester, epoxy, or unsaturatedpolyester components. The urethane component is from 10 to 50 wt. %based on the amount of gel coat. The urethane and vinyl ester, epoxy, orunsaturated polyester reactants are combined under conditions effectiveto cure both components in the same cure cycle.

“Co-cured” means that the reactions involved in producing a urethanepolymer (i.e., reaction of a polyisocyanate or NCO-terminated prepolymerwith polyols and hydroxy or amine-functional extenders) take placeessentially concurrently with reactions involved in converting vinylester, epoxy, or unsaturated polyester reactants to cured products.Unsaturated polyester and vinyl ester resins generally react withstyrene and free-radical initiators to produce a cured thermosetpolyester or vinyl ester. Epoxy resins generally react with “hardeners”or curing agents to produce a cured epoxy component. The co-curedproduct comprising the urethane and polyester, epoxy, or vinyl estercomponents is distinguishable from an interpenetrating network (IPN)because there can be some reactions involving chains of each network.

The urethane component is generated from any desired combination ofurethane reactants, including polyisocyanates, isocyanate-terminatedprepolymers, polyols, and chain extenders, all of which are well knownand commercially available. The polyisocyanate can be aromatic oraliphatic. Aromatic polyisocyanates include, e.g., toluene diisocyanates(TDI), 4,4′-diphenylmethane diisocyanates (MDI), or polymericdiisocyanates (PMDI), or the like. Aliphatic polyisocyanates include,e.g., hexamethylene diisocyanate (HDI), hydrogenated MDI, cyclohexanediisocyanate (CHDI), isophorone diisocyanate (IPDI), trimethyl ortetramethylhexamethylene diisocyanate (TMXDI), or the like.Isocyanate-terminated prepolymers are made with any of the abovepolyisocyanates and a polyol; many prepolymers are commerciallyavailable. Suitable polyols have molecular weights from 500 to 10,000and functionalities from 2 to 6. Typically, these are hydroxyl oramine-terminated polyether or polyester polyols, most commonly apolyether or polyester diol or triol. The polyol can have higherfunctionalities, as in alkoxylated sucrose polyols or the like. Suitablechain extenders are usually low-molecular-weight diols or diamines suchas ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol,ethylene diamine, 4,4′-methylene-bis(2-chloroaniline) (“MOCA”), and thelike. The urethane system can be a one- or two-component system. It canbe a pure urethane system (i.e., hydroxyl-terminated reactants only), apolyurea (amine-terminated polyols and/or amine extenders), or acombination or mixture of these. For more information about reactantsand processes used to make urethane polymers, see W. F. Gum, W. Riese,and H. Ulrich, Reaction Polymers: Polyurethanes, Epoxies, UnsaturatedPolyesters, Phenolics, Special Polymers, and Additives; Chemistry,Technology, Applications, Markets, Hanser Publishers, NY (1992),especially pp. 50-124.

We found that for purposes of practicing this invention, it is possibleand convenient to use fully formulated polyurethane and/or polyureaproducts. Numerous examples below, for instance, utilize Selby™ N300 CR(product of BASF), a two-component polyurethane based on an aliphaticpolyisocyanate and designed for use as a floor coating or itscombination with EnviroLastic® resin (product of Sherwin-Williams) orLine-X® resin (Line-X, Inc.), polyureas commonly used to coat truck bedliners. Of course, the skilled person has discretion to customize orformulate the urethane and or urea from the usual building blocks or tosimply use commercially available products.

The urethane component is from 10 to 50 wt. %, preferably from 10 to 25wt. %, based on the amount of gel coat. We surprisingly found that suchlevels of urethane in the gel coat impart substantial toughness anddurability to the gel coat such that cracks and chips can be avoided.This is particularly important in marine applications, where current gelcoat technology is limiting due to its brittle nature.

The gel coat also comprises an unsaturated polyester, epoxy, or vinylester component. When this component is a polyester or vinyl ester, itis usually generated by combining an unsaturated polyester resin orvinyl ester resin with an ethylenic monomer, usually styrene, and afree-radical initiator. The unsaturated polyester, epoxy, or vinyl estercomponent of the inventive gel coat can be a conventional gel coatformulation.

Suitable unsaturated polyester resins are well known. They are generallypolymers of intermediate molecular weight made by condensing glycols,maleic anhydride, and dicarboxylic acids (or their anhydrides) to give aresin having a targeted acid number. Typical glycols include ethyleneglycol, propylene glycol, diethylene glycol, dipropylene glycol,alkoxylated bisphenol A, cyclohexane dimethanol, neopentyl glycol, andthe like. The dicarboxylic acid or anhydride can be aromatic, aliphatic,or a mixture of these. Typical examples include phthalic anhydride,isophthalic acid, terephthalic acid, adipic acid, succinic acid,tetrabromophthalic anhydride, tetrahydrophthalic anhydride, maleic acid,fumaric acid, and the like. Maleic anhydride is used to provide acrosslinkable carbon-carbon double bond capable of reacting with theethylenic monomer in the presence of the free-radical initiator.

Suitable ethylenic monomers include, for example styrene,α-methylstyrene, divinylbenzene, methyl methacrylate, butyl acrylate,vinyl toluene, and the like, or their mixtures. Styrene is preferred.

Preferred unsaturated polyester resins for use in gel coats are based onisophthalic acid, particularly resins formulated from maleic anhydride,isophthalic acid, and neopentyl glycol.

The unsaturated polyester resin can be formulated from the startingmaterials described above or it can be obtained commercially. Suppliersof suitable unsaturated polyester resins include, for example, CCPPolymers, Interplastic Corporation, Reichhold, Ashland, and others.

For more details about how to make and use unsaturated polyester resins,see W. F. Gum et al., Reaction Polymers, supra, at pp. 153-202.

The vinyl ester component, when used, is normally a reaction product ofan epoxy resin and an unsaturated carboxylic acid (typically acrylicacid, methacrylic acid, or the like). Epoxide end groups of the epoxyresin react with the hydroxyl group of the unsaturated carboxylic acidto give a resin having terminal unsaturation that is conjugated with anester carbonyl group. The crosslink density of the cured vinyl ester iscontrolled by selecting an epoxy resin of desirable molecular weight andpolydispersity. In a typical example, an epoxy resin made reactingbisphenol A with epichlorohydrin is further reacted with enoughmethacrylic acid to convert the epoxide end groups to vinyl estergroups. The same free-radical initiators used to cure unsaturatedpolyesters are also used to make the vinyl ester component. For moredetails, see W. F. Gum et al., Reaction Polymers, supra, at pp. 190-194and U.S. Pat. Nos. 3,367,992; 3,996,307; 4,197,390; and 4,296,220, theteachings of which are incorporated herein by reference.

Vinyl ester resins and systems are commercially available from AOC,Ashland, Interplastic, Reichhold, Dow Chemical, and other suppliers.

The epoxy component, when used, is usually made by reacting an epoxyresin—often a diglycidyl ether reaction product of bisphenol A withepichlorohydrin—with a hardener or curing agent such as an aromaticdiamine.

Many suitable epoxy resins and curatives are commercially available fromDow Chemical, Huntsman, Royce International, Momentive SpecialtyChemicals, West, MAS, Interlux, and others.

Suitable curatives for epoxy resins include, for example, aliphaticamines, cycloaliphatic amines, aromatic amines, polyamides, amidoamines,polysulfides, anhydrides, and the like.

For more examples of epoxy resin classes and curing agents, see W. F.Gum et al., Reaction Polymers, supra, at pp. 125-153 and U.S. Pat. Nos.7,217,771; 6,660,373; 5,919,844; and 5,872,196, the teachings of whichare incorporated herein by reference.

The manner in which the urethane and polyester, vinyl ester, or epoxyreactants are combined to produce the gel coats is generally notcritical and is left to the discretion of the skilled person. There maybe advantages, for instance, to minimizing the number of reactantstreams by pre-combining certain components that will not react, thencontacting the reactant streams in one shot to produce the co-curedsystem. We surprisingly found, e.g., that one can simply mix commercialurethane and urea systems with a commercial vinyl ester resin andachieve good results.

The inventive gel coats offer important advantages. Including theurethane component improves toughness, flexibility, and durability sothe gel coat is long-lasting and resists cracking and chipping. Incontrast to urethane coatings, the gel coats can be applied using anin-mold process while maintaining good adhesion with structural layers.Because the amount of urethane is easily varied, the formulator can useenough urethane to impart needed toughness but also limit the amount ofurethane to retain stiffness and keep costs within budget. In someapplications, surface appearance is a prime consideration, and theamount of urethane will generally be minimized. For applications notrequiring a perfect surface, however, there may be advantages to using arelatively high proportion of urethane to maximize flexibility orresilience.

End-use applications for the gel coats include many fiber-reinforcedcomposite structures that require a smooth, durable outer surface,particularly products produced using an in-mold process. Examplesinclude marine, aircraft, construction, kitchen and bath, wind energy,and other applications.

In another aspect, the invention relates to an elastomeric coating. Likethe gel coats described previously, the elastomeric coating alsocomprises co-cured urethane and vinyl ester, epoxy, or unsaturatedpolyester components, where “co-cured” has the meaning ascribed above.The urethane and vinyl ester, epoxy, or unsaturated polyester componentsare combined and reacted under conditions effective to cure bothcomponents in the same cure cycle. The urethane, vinyl ester, epoxy, andunsaturated polyester components used to make the elastomeric coatingare the same ones described previously. The elastomeric coatings,however, have high urethane content. In particular, the urethanecomponent is from 50 to 95 wt. %, preferably 70 to 90 wt. %, based onthe amount of elastomeric coating.

The higher urethane content of the elastomeric coating (compared withthe gel coat) makes the coating well-suited for applications that demandgreater resilience and flexibility but not necessarily a smooth, glossysurface. Such coatings can be valuable for a submarine bow dome, forinstance, where durability trumps appearance. The minor proportion ofunsaturated polyester, epoxy, or vinyl ester in the elastomeric coatingenables good adhesion to structural layers, so the potential peelingissues of a post-applied polyurethane coating, particularly underhigh-stress, hydrodynamic conditions, can be avoided. Moreover, unliketraditional polyurethane coatings, the elastomeric coating can be usedin an in-mold process as is used for gel coatings.

As was the case with the inventive gel coats, the manner in whichreactants are combined for making the elastomeric coatings is notconsidered critical and is left the skilled person's discretion.

Other potential end-uses for the elastomeric coatings includeapplications that can benefit from having a flexible, strong outerlayer. Examples include marine applications, recreational vehicles,roofing, exterior wall coating, parking structures, cooling towers, andthe like.

The invention includes laminates made from the elastomeric coatings orgel coats and one or more structural layers. Laminates include one ormore structural layers, at least one of which is bonded to the inventivegel coat or elastomeric coating. Preferably, the structural layer orlayers are the inventive structural layers discussed immediately below.

In one aspect, the invention relates to a casting. The casting, whichmay be reinforced, comprises co-cured urethane and vinyl ester, epoxy,or unsaturated polyester components. The urethane component is from 10to 95 wt. %, preferably from 10 to 50 wt. %, based on the amount ofcasting, and the urethane and vinyl ester, epoxy, or unsaturatedpolyester reactants are combined under conditions effective to cure bothcomponents in the same cure cycle. For examples of some unreinforcedcastings, see Table 1 below. We surprisingly found, for instance, thatdespite the known flexibility of an all-urethane system, incorporationof 25 wt. % of co-cured urethane into a vinyl ester system increasesboth tensile strength and stiffness compared with the 100% vinyl estersystem.

In another aspect, the invention relates to a structural layercomprising a reinforced thermoset. The thermoset comprises co-curedurethane and vinyl ester, epoxy, or unsaturated polyester components,where “co-cured” has the meaning ascribed above. The urethane and vinylester, epoxy, or unsaturated polyester components are combined andreacted under conditions effective to cure both components in the samecure cycle. The urethane, vinyl ester, and unsaturated polyestercomponents used to make the structural layer are the same ones describedpreviously. The urethane component is from 10 to 95 wt. %, preferablyfrom 25 to 75 wt. %, based on the amount of thermoset.

The structural layer is a composite material. It comprises a co-curedresin and reinforcing material. Reinforcement can be in any desiredsuitable form, such as fibers, fabric, mats, chopped pieces, particles,or the like. The reinforcement can be chopped glass, glass strands, SMCgrinds, silicon carbide, quartz, graphite, fiberglass, organic polymers,cellulose fibers, polyamide fibers, polypropylene fibers, carbon fibers,boron fibers, inorganic materials, or the like. Other suitablereinforcing materials are described in U.S. Pat. Nos. 4,921,658 and6,780,923, the teachings of which are incorporated herein by reference.

The traditional approach of applying multiple structural layers ofpolyester or vinyl ester can be used. Because the inventive structurallayers have urethane content, they can have improved flexibility andtoughness compared with the reinforced polyester, epoxy, or vinyl esterlayers. Moreover, the structural layers adhere well to each other and totraditional coatings or the inventive gel coats and elastomericcoatings, so delamination or peeling is avoided.

In one aspect, the invention relates to a laminate comprising two ormore of the inventive structural layers described above, wherein eachstructural layer comprises urethane and vinyl ester, epoxy, orunsaturated polyester components. The layers can be arranged in anydesired order to optimize properties. Various combinations might beemployed, for instance to include a viscoelastic layer useful fordamping, a layer having shock-absorbing properties, or a layer sequencethat optimizes acoustic properties of the laminate.

Urethane content can be “dialed in” for each layer, so multilayerlaminates can be fabricated that have a desired gradient of flexibility,toughness, tensile strength, elongation, and other important properties.For instance, a material that has a highly flexible exterior but stifferinner layers could be made using an elastomeric coating of the inventionas an outer coat, followed by a structural layer ofpolypropylene-reinforced resin with 50 wt. % urethane, followed by astructural layer of glass fiber-reinforced resin with 25 wt. % urethane,followed by an inner layer of carbon fiber-reinforced vinyl ester resin.

In another aspect, the invention relates to a multilayer laminatecomprising two or more of the inventive structural layers describedabove, wherein each structural layer comprises urethane and vinyl ester,epoxy, or unsaturated polyester components, and each successivestructural layer comprises progressively more of the urethane component.

Thus, in some applications, it might be more desirable to have greaterflexibility in the innermost layers of a multilayer laminate, so theordering can be reversed. Thus, after applying a traditional gel coat,structural layers having progressively more urethane could be applied tobuild more flexibility into the inner part of the multilayer structure.

The ability to control the amount of urethane in each layer whilemaintaining good interlayer adhesion provides a unique opportunity tocontrol the degree of elongation of each reinforced structural layer andidentify structures with the most desirable balance of physical andmechanical properties.

The structural layers are usually non-cellular, but if desired, ablowing agent can be included to impart a cellular or microcellularstructure. It is also possible to utilize structural layers comprising arigid, semi-rigid, or flexible foam as part or all of the layer. Foamsare particularly desirable in applications for which weight reduction isimportant, as in the marine, automotive, or aerospace industries.

In another aspect, the invention relates to an in-mold process formaking a laminate. The process comprises applying to a mold a layer ofco-curable gel coat formulation. The gel coat formulation comprises theurethane and vinyl ester, epoxy, or unsaturated polyester componentsdescribed earlier. The urethane component is from 10-50 wt. % based onthe amount of gel coat formulation. Before or after the gel coat layercures, at least one structural layer is applied to the gel coat layer,and the layers are allowed to cure to produce the laminate. Preferably,the structural layer is an inventive structural layer as describedherein comprising co-cured urethane and unsaturated polyester, epoxy, orvinyl ester components. Typically, structural layers are applied afterthe gel coat layer has substantially cured.

In another aspect, the invention relates to an in-mold process formaking a laminate. The process comprises applying to a mold a layer of aco-curable elastomeric coating formulation. The elastomeric coatingcomprises the urethane and the vinyl ester, epoxy, or unsaturatedpolyester components (including possibly a conventional gel coat)described earlier. The urethane component is from 50-95 wt. % based onthe amount of elastomeric coating. Before or after the elastomericcoating layer cures, at least one structural layer is applied to theelastomeric coating layer, and the layers are allowed to cure to producethe laminate. Preferably, the structural layer is an inventivestructural layer as described herein comprising co-cured urethane andunsaturated polyester, epoxy, or vinyl ester components. Typically,structural layers are applied after the elastomeric coating layer hassubstantially cured.

In yet another aspect, the invention relates to an in-mold process formaking a laminate. The process comprises applying to a mold a layer of agel coat formulation, typically a conventional gel coat. Before or afterthe gel coat layer cures, typically thereafter, at least one structurallayer is applied to the gel coat layer, and the layers are allowed tocure to produce the laminate. The structural layer comprises areinforced thermosetable composition. The thermosetable compositioncomprises co-curable urethane and vinyl ester, epoxy, or unsaturatedpolyester components. The urethane component is from 10 to 95 wt. %based on the amount of thermosetable composition, and the urethane andvinyl ester, epoxy, or unsaturated polyester reactants are combinedunder conditions effective to cure both components in the same curecycle.

In an exemplary application, the inventive elastomeric coatings and/orstructural layers are used to construct a fiber-reinforced plastic sonardome for a naval vessel, e.g., a submarine (see, e.g., U.S. Pat. Nos.4,997,705 and 7,638,085, the teachings of which are incorporated hereinby reference). The inventive compositions impart good acousticperformance, high strength to weight ratio, good fatigue and impactresistance, good noise and vibration damping, corrosion resistance, andease of maintenance to the sonar dome.

Like other marine composite structures, the multilayer structure of asonar dome must be able to withstand substantial out-of-plane loadscaused by wave slamming, localized impacts, and other shock events. Theouter surfaces need to handle increased strain rates to help the stifferinner layers contribute to the structure's robustness. By transitioningthe modulus of the structure from lower to higher values in multiplelayers, interlaminar loads can be reduced, the entire laminate canfunction as one system, and optimum performance, damping, andsurvivability can be achieved.

The inventive coatings and structural layers can meet the challengesnoted above because strain to failure values can be adjusted fromelastomeric (>100% strain to failure) to that of a conventional vinylester resin (5-7% strain to failure), typically by simply adjustingurethane content. Thus, a multilayer laminate can be optimizedply-by-ply to give optimized toughness and strain to failure throughoutthe structure. High-strain (elastomeric) plies can be used on exteriorsurfaces, while stiffer plies can be used as the neutral axis (minimumdisplacement under stress) of the structure is approached.

The robustness, acoustic properties, cost, and other aspects of thesonar dome can be further controlled by altering the nature of thereinforcing material, including the fabric architecture, fiber type, andother factors. Fibers and fabrics can be selected and combined,comingled, or oriented to optimize any of these benefits. For instance,organic polymer fibers such as polypropylene might be used incombination with glass and/or carbon fibers. For further discussion ofhow to optimize acoustic performance with blended yarns and fabrics, seeU.S. Pat. No. 7,638,085.

The process used to manufacture the dome will also have an impact onproperties and cost. Preferably, resin infusion methods such asvacuum-assisted resin-transfer molding are used. A multicure infusionprocess, which allows production of optimized structures, isparticularly preferred. Vacuum-assisted resin-transfer molding is acost-effective alternative to conventional pre-impregnation techniques(see, e.g., U.S. Pat. Nos. 7,980,840; 7,189,345, and 6,159,414, theteachings of which are incorporated herein by reference).

For example, the outer surface of the sonar dome can be an unreinforcedelastomeric coating of the invention comprising 50-95 wt. %, preferablyfrom 75 to 90 wt. %, of the urethane component. Next, a series ofstructural layers comprising optimized fabrics can be placed over theelastomeric coating and infused with a high strain to failure (i.e.,elastomeric) resin. The next series of optimized structural layers wouldcomprise fabrics placed and infused with a lower strain to failure (butstiffer) resin. The layering process continues until the structure'sneutral axis is reached, after which the infusions would use fabrics andresins suited for progressively higher strain to failure. Thiscost-effective strategy provides a sonar dome having optimum acousticand damping properties, impact resistance, and survivability.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

Example A

A commercial vinyl ester resin, CoREZYN® VE8121 (product ofInterplastic), is stirred with MEKP/Co catalyst at room temperature. Atthe same time, the A and B components of Selby™ N300 CR, a two-parturethane floor coating (product of BASF) are combined at roomtemperature. The catalyzed vinyl ester and urethane components arequickly mixed (50:50 weight ratio), and the mixture is brushed onto amold and allowed to cure. After the coating cures, a conventional skincoat of polyester resin is applied, and thereafter, additionalstructural layers are laminated. The fully cured sample is removed fromthe mold. It has excellent adhesion and elasticity. Excellent adhesionis also demonstrated with co-cured 25 wt. % urethane/75 wt. % vinylester as the in-mold gel coating. This sample is somewhat less elasticthan the sample having the 50/50 urethane/vinyl ester blend as the gelcoating.

In contrast, when a 100% urethane gel coat is applied and cured,followed by application of a conventional skin coat of polyester resinand additional structural layers, the fully cured product demonstratespoor adhesion of the urethane coating to the structural layers.

Co-Cured Castings

CoREZYN® VE8121 resin (Interplastic) is stirred with MEKP/Co catalyst atroom temperature. At the same time, the A and B components of Selby™N300 CR are combined and stirred briefly at room temperature. Thecatalyzed vinyl ester and urethane resins are then quickly combined,mixed well, poured into a mold, and allowed to cure. Properties of theresulting unreinforced castings appear in Table 1.

TABLE 1 Co-cured Castings Tensile Ex VE8121 PU strength ModulusElongation Shore A # (wt. %) (wt. %) (psi) (kpsi) (%) hardness C1 100 02100 120 2.1 — 2 75 25 6500 710 1.0 — 3 25 75 650 3.7 16 93 4 12.5 87.5400 1.1 38 81 VE8121 = CoREZYN ® VE8121, a vinyl ester resin(Interplastic). PU = Selby ™ N300 CR urethane (BASF).

The results in Table 1 illustrate the wide variety of propertiesavailable depending upon the proportion of urethane included in theco-cured system. Note the substantial increase in tensile strength uponinclusion of just 25 wt. % urethane (Example 2 versus ComparativeExample 1). The nature of the product changes dramatically (to softermaterials) when the urethane is the major component of the co-curedsystem (Examples 3 and 4).

Coated Laminates

Test laminates are constructed using Maxguard® 33LE-2435 UV grey(Ashland), which is a conventional polyester gel coat (ComparativeExample 5), or co-cured blends of a vinyl ester resin with aurethane/urea combination (Examples 6 and 7). Except for the coatingformulation, all of the laminates are prepared using the same base resinand procedure. The laminates are tested for flexural modulus andstrength properties in accord with ASTM D790. All samples are tested atthe same support span. The stress level, the deflection at the time ofcoating crack appearance, and the ultimate stress levels are recorded.Results appear in Table 2.

TABLE 2 Coated Laminates: Three-Point Bend Results¹ Stress at DeflectionStrain at coating at coating coating Ex. crack crack crack # Coating(wt. %) (kpsi) (in) (in/in) C5   Polyester gel coat (100) 19.0 0.14 — 6PU (12.5)/urea (12.5)/VE8106 (75) 23.5 0.34 0.03 7 PU (25)/urea(25)A/E8106 (50) 24.7 0.40 0.04 Polyester gel coat = Maxguard ®33LE-2435 UV grey (Ashland) PU = Selby ™ N300 CR (BASF); urea =EnviroLastic ® polyurea resin (Sherwin-Williams). VE8106 = CoREZYN ®VE8106, a vinyl ester resin (Interplastic). ¹ASTM D790; support tospecimen depth ratio = 16:1. Values represent an average of 6 testspecimens.

Ideally, the coating only cracks when the rest of the structure fails.As Table 2 shows, when a polyester gel coat alone is used to coat thelaminate (Comparative Example 5), the coating cracks early, i.e., beforethe laminate cracks. In Examples 6 and 7, the coating crackssimultaneously with the laminate. At 25 wt. % urethane/urea, theformulation is a modified gel coat (Example 6), while at 50 wt. %urethane/urea, the formulation is better characterized as an elastomericcoating (Example 7).

Additional Coated Laminates

Test laminates are constructed using the conventional polyester gelcoat, co-cured blends of the polyester gel coat with urethane, andco-cured blends of a vinyl ester resin with urethane. Except for thecoating formulation, all of the laminates are prepared using the samebase resin and procedure. The laminates are tested for flexural andstrength properties in accord with ASTM D790. All samples are tested atthe same support span. The stress level, the deflection at the time ofcoating crack appearance, and the ultimate stress levels are recorded.Results appear in Table 3.

TABLE 3 Coated Laminates: Three-Point Bend Results¹ Stress at Deflectioncoating Maximum at coating Ex. crack stress crack # Coating (kpsi)(kpsi) (in) C5   Polyester gel coat (100) 19.0 23.5 0.14 8 PU(25)/polyester gel coat (75) 30.7 30.9 0.27 9 PU (50)/polyester gel coat(50) 29.5 29.7 0.29 10  PU (75)/polyester gel coat (25) 26.8 27.2 0.2811  PU (75)/VE8123 (25) — — 0.27 Polyester gel coat = Maxguard ®33LE-2435 UV grey (Ashland) PU = Selby ™ N300 CR (BASF); CoREZYN ®VE8123 is a vinyl ester resin (Interplastic). ¹ASTM D790; support tospecimen depth ratio = 16:1. Values represent an average of 6 testspecimens.

Co-curing the urethane and polyester gel coat gives a coated laminatehaving a substantial increase in deflection at coating crack. When nourethane is present, the gel coat cracks before the laminate fails(Comparative Example 5). In contrast, when 25 wt. % or more urethane isused, the laminate fails at the same time as, or prior to, failure ofthe coating (Examples 8-11). In co-cured Examples 8-10, the stress atcoating crack generally coincides with the maximum stress, soincorporation of the urethane allows for development of full laminatestrength. Example 11 shows that the improvement in deflection at coatingcrack is consistent whether a polyester gel coat or a vinyl ester isused. With 75 wt. % urethane, Examples 10 and 11 are elastomericcoatings. Example 8 (25 wt. % urethane) is a gel coating; Example 9borders between the two types.

Evaluation of Coating Adhesion Upon Estuary Exposure

Coated laminates are evaluated for adhesion performance followingimmersion in an estuary environment. Thus, laminates are preparedaccording to a common procedure and placed in the Indian River Lagoon, asection of the Intracoastal Waterway, east of Melbourne, Fla. Adhesiontesting is performed according to ASTM D4541 on samples prior toexposure and after three or six months of exposure to the estuary.Results appear in Table 4.

TABLE 4 Adhesion of Coated Laminates upon Estuary Exposure Adhesivestrength by ASTM D4541 (psi) Ex. Un- 3-Month 6-Month # Coating exposedExposure Exposure C12 Polyester gel coat (100) 1011 917 735 C13EnviroLastic ® polyurea 416 512 511 (100) C14 Line-X ® polyurea (100)864 866 594   15 PU (50)/VE8123 (50) 1070 1005 908   16 PU(50)/polyester gel coat 1226 1387 1706 (50) Polyester gel coat =Maxguard ® 33LE-2435 UV grey (Ashland) PU = Selby ™ N300 CR (BASF);CoREZYN ® VE8123 is a vinyl ester resin (Interplastic); EnviroLastic ®polyurea resin (Sherwin-Williams); Line-X ® protective coating (Line-X,Inc.).

The conventional gel coat (Comparative Example 12) shows significantdegradation of coating adhesion over time upon exposure to estuary water(˜27% loss of adhesive strength after six months). The polyurea coatings(Comparative Examples 13 and 14) have lower adhesive strength andexhibit the lowest values after six-month water exposure. In contrast,the urethane/vinyl ester and urethane/polyester gel coat co-cures(Examples 15 and 16, respectively) demonstrate better initial adhesionand a reduced degree of degradation upon three- or six-month exposure tothe estuary. The results with the urethane/polyester gel coat areparticularly remarkable, as this co-cure not only shows the best overalladhesion, but the adhesive strength actually increases, and does sodramatically (almost 40%), upon six-month water exposure.

The preceding examples are meant only as illustrations. The followingclaims define the invention.

I claim:
 1. A gel coat comprising co-cured polyurethane and vinyl ester,epoxy, or non-hydroxyl-terminated unsaturated polyester components,wherein the ratio of the polyurethane component to the vinyl ester,epoxy, or polyester component, or combination thereof is from 10:90 to50:50 by weight.
 2. A curable composition comprising a mixture of (a)one or more polyisocyanate components; (b) one or more polyolcomponents; and (c) one or more vinyl ester, epoxy, or unsaturatedpolyester components, or a combination thereof; wherein the ratio of (a)and (b) to (c) is from 10:90 to 50:50 by weight and where thecomposition is adapted for preparing polyurethane.
 3. The curablecomposition of claim 2 wherein the ratio of (a) and (b) to (c) is from10:90 to 25:75 by weight.
 4. The curable composition of claim 2 whereinthe ratio of (a) and (b) to (c) is from 10:90 to 20:80 by weight.
 5. Thecurable composition of claim 2 wherein the ratio of (a) and (b) to (c)is from 10:90 to 15:85 by weight.
 6. The curable composition of claim 2wherein the polyisocyanate component comprises an aliphaticpolyisocyanate.
 7. The curable composition of claim 2 wherein thepolyisocyanate component comprises hexamethylene diisocyanate,hydrogenated 4,4′-diphenylmethane diisocyanates, cyclohexanediisocyanate, isophorone diisocyanate, trimethylhexamethylenediisocyanate, or tetramethylhexamethylene diisocyanate, or a combinationthereof.
 8. The curable composition of claim 2 comprising the polyestercomponent.
 9. The curable composition of claim 8 wherein the polyestercomponent comprises a polymer made from one or more glycols includingneopentyl glycol, and one or more dicarboxylic acids.
 10. The curablecomposition of claim 8 wherein the polyester component comprises apolymer made from one or more glycols, and one or more dicarboxylicacids including isophthalic acid or maleic anhydride, or a combinationthereof.
 11. The curable composition of claim 8 wherein the polyestercomponent comprises a polymer made from maleic anhydride, isophthalicacid, and neopentyl glycol.
 12. The curable composition of claim 8wherein the polyester component comprises styrene.
 13. The curablecomposition of claim 2 comprising the vinyl ester component.
 14. Thecurable composition of claim 13 wherein the vinyl ester componentcomprises a polymer made from bisphenol A, epichlorohydrin, andmethacrylic acid.
 15. The curable composition of claim 13 wherein thevinyl ester component comprises styrene.
 16. A composition comprisingthe cured reaction products of the curable composition of claim
 2. 17. Acomposition comprising a gel coat prepared by contemporaneously curingthe curable composition of claim
 2. 18. A laminate comprising thecomposition of claim 17 and a structural layer.
 19. The laminate ofclaim 18 wherein the structural layer comprises a cured resin and areinforcing material.
 20. The laminate of claim 19 wherein thereinforcing material comprises chopped glass, glass strands, SMC grinds,silicon carbide, quartz, graphite, fiberglass, organic polymers,cellulose fibers, polyamide fibers, polypropylene fibers, carbon fibers,boron fibers, or inorganic materials, or a combination thereof.
 21. Thelaminate of claim 19 wherein the resin comprises a curable compositioncomprising a mixture of (x) one or more polyisocyanate components; (y)one or more polyol components; and (z) one or more vinyl ester, epoxy,or unsaturated polyester components, or a combination thereof; whereinthe ratio of (x) and (y) to (z) is from 10:90 to 50:50 by weight. 22.The laminate of claim 21 wherein the ratio of (x) and (y) to (z) in theresin is equal to or less than the ratio of (a) and (b) to (c) in thecurable composition.
 23. A kit comprising (a) one or more polyisocyanatecomponents; (b) one or more polyol components; (c) one or more vinylester, epoxy, or unsaturated polyester components, or a combinationthereof; and (d) instructions for mixing (a), (b), and (c) in a ratio of(a) and (b) to (c) in the range from 10:90 to 50:50 by weight; andcontemporaneously curing the mixture of (a), (b), and (c) to preparepolyurethane.
 24. The kit of claim 23 wherein (b) and (c) are a mixture.25. The kit of claim 23 wherein the mixture is cured to form a gel coat.26. The kit of claim 23 further comprising instructions for applying(a), (b), and (c) to a mold.